Concrete colourants

ABSTRACT

A method of colouring cementitious building materials such as concrete is disclosed. The method uses flowable, spray-dried, particulate formulations of inorganic pigments prepared using a selection of formulants that do not substantially effect primary ettringite formation. Quantities of the formulations may conveniently be dispensed into a slurry of cement and water by gravimetric or volumetric means.

FIELD OF INVENTION

The invention relates to methods of colouring cementitious buildingmaterials, such as concrete, and formulations for use in these methods.In particular, the invention relates to a method of colouring concreteused in floor levelling and repair.

BACKGROUND ART

Cementitious building materials such as concrete are used in largevolumes throughout the world. By varying the proportions of ingredientsused in the cementitious premix, many types of concrete are available.These include floor levelling and repair products. Such products areused, for example, in preparing a floor prior to the laying of acovering such as carpet or vinyl. These products are designed to findtheir own levels when installed at a thickness of 3 mm or greater. Oncehydrated and poured the cementitious mix hardens and sets rapidly sothat it can be walked on within as little as two to three hours. It isoften desired to improve the aesthetic qualities of building materialsby introducing colour. To achieve this the surface of the buildingmaterial may be either dyed or colour added during the forming of thematerial (referred to here as “integral colouring”).

As discussed in the publication of Hertz et al (2012) several methodsfor dyeing a concrete surface are known. A first method involves washingthe surface with an acidic solution containing a metal salt. Followingdevelopment of the colour a neutralising agent, then a clear protectivepolymeric sealing coating are applied. A second method involves washingthe surface with an acidic solution to roughen or etch the surfacebefore colouring the surface with a polymer based stain or paint andfinishing with a clear coating. A third method involves etching orgrinding the surface before applying a cementitious overlay. Thecementitious overlay is then stained with an acidic solution containinga metal salt. These methods are generally disadvantageous due to the useof highly corrosive acidic solutions which are hazardous to handle.

Historically, the integral colouring of concrete has been achieved byadding formulations of inorganic pigments such as iron oxide to thehydrated premix. A range of earth tones are thereby obtainable.Ingredients used in the cementitious premix, such as those added toprovide integral colour or the requisite “self-levelling” properties offloor levelling and repair products, must not adversely affect thedurability and strength of the building material once formed.Furthermore, ingredients added to a cementitious premix to providecolour should not interfere with the function of additives included, forexample, to provide “self-levelling” properties. By way of illustration,inorganic pigments such as iron oxide can inhibit the performance ofshrinkage-compensating additives used in floor levelling and repairproducts resulting in cracking. Many different formulations of pigmentshave been proposed for integral colouring of cementitious buildingmaterials, especially concrete.

The publication of Tomkinson (1971) discloses colouring materialsdeposited on iron oxide particles obtained by precipitation. Preferredcolouring materials include carbon black, azo colouring materials, vatdyes (anthraquinoid and indigoid) and phthalocyanine colouringmaterials. The pigments thereby provided are proposed for use incolouring concrete, tile and brick.

The publication of Bowen (1980) states that it is difficult to obtain asufficiently thorough mixing of powders into a wet cement mix so as toachieve a homogenous colour throughout the mixture. The publicationdiscloses stabilized thixotropic slurries for colouring concretecomprising pigment, at least one stabilizer, a dispersant and water.

The publication of Jungk (1990) discloses granules for use in colouringconcrete consisting of one or more pigments and one or more binders forpromoting the dispersing of the pigments in the concrete. Ammoniumlignin sulfonated powder is used as the binder.

The publication of Krockert and Linde (1993) discloses a process forcolouring building materials. The process uses inorganic pigments (ironoxides, titanium oxide) formulated as granules. The granules areprepared by spray-drying aqueous suspensions of 38 to 55% by weight ofthe inorganic pigments and 0.3 to 1.3% by weight of soluble salts. Thegranules are asserted to have at least satisfactory flow behaviour andrapid dispersibility in concrete.

The publication of Linde and Eitel (1996) discloses a process for thecolouration of building materials such as concrete by granulatedinorganic pigments. The commercially available formulations of inorganicpigments (Bayer AG) are mixed with a small amount of machine orvegetable oil, compacted and then granulated to provide material with agrain size of 0.2 to 2 mm.

The publication of Kohler et al (1998) discloses a process for thepreparation of iron oxide black pigment granules which are stable tohandling. The process includes a step of tempering spray-dried granulesof iron oxide black pigment in an indirectly heated rotary kiln attemperatures below 65° C. in an inert nitrogen atmosphere forapproximately 30 to 60 minutes. The granules are asserted to have highstrength, dispersibility and stability to oxidation.

The publication of Will (1998) discusses how many inorganic pigments,such as metal oxides, do not disperse well in cementitious systems. Thepublication discloses a method for colouring cementitious systems usingcompacted inorganic granules. The compacted inorganic granules comprisean inorganic pigment and a dispersing agent.

The publication of Johansen et al (1999) discloses an aqueouscomposition for colouring cement-based composition comprising water,pigment, a suspension enhancing agent and latex polymer solids. Amixture of predetermined amounts of a cement-based component and theaqueous composition is asserted to provide a cement-based composition ofuniform and standardised colour that is capable of being consistentlyreproduced.

The publication of Supplee (2003) discloses a composition for colouringconcrete. In addition to the colourant the composition includes astearic acid, salt or derivative as a hydrophobic efflorescence controlagent. The composition also includes particulated polymers andco-polymers. The composition is asserted to improve durability of thecoloured concrete.

The publication of Dunnous and Yocum (2004) discloses pigment-containinggranules for use in colouring concrete. The publication states thatforming granules with a soluble organic binder by spray-drying can beproblematic due to the high temperature air flow used. It is assertedthat if charring of the soluble organic binder occurs it will no longerbe readily soluble in water. This technical problem is avoided in themethod disclosed by using an insoluble, pozzolanic clay (aluminiumsilicate) agglomerator.

The publication of Noack and Herrmann (2004) discloses colouring pigmentgranulates. The granulates comprise granulated cores that do not containbinders, emulsifying agents, surface active agents, dispersing agents,or preservatives. The granulates cores are enclosed by an envelopinglayer made of a material such as polyvinyl alcohol, that can be brokendown. The absence of binders and other auxiliaries is asserted to ensurerapid disagglomeration once the shell enveloping material is brokendown.

The publication of Supplee (2007) discloses compositions for colouringconcrete when integrally or surface-shake applied. The compositioncomprises a spray-dried styrene acrylic polymer encapsulated colourantand a second polymer for use in dispersing the encapsulated colourant.

The standard of Anon (2010) prescribes that coloured concrete pigmentedat a maximum dosage rate of 10% by weight of the cement shall have a28-day compressive strength of not less than 90% and a water to cementratio of not greater than 110% of that of the control. The standardfurther prescribes that when added to concrete at the maximum dosagerate, the pigment is to neither accelerate the initial or final set bymore than one hour nor retard the initial or final set by more than oneand a half hours, and the air content is not be changed by more than 1%as compared to the control.

It is an object of the invention to provide a method of colouringconcrete capable of complying with the requirements of the standard ofAnon (2010). It is an object of the invention to provide colourants foruse in the method. These objects are to be read disjunctively with theobject to provide at least a useful choice in the colouring ofcementitious building materials.

STATEMENT OF INVENTION

In a first aspect the invention provides a flowable, spray dried,particulate formulation suitable for use in colouring cementitiousbuilding materials comprising in admixture one or more inorganicpigments, poly(ethylene glycol), hydroxylated amine and polycarboxylicacid.

Preferably, the one or more pigments of the formulation are inorganicpigments selected from the group consisting of: synthetic iron oxides(black, browns, red and yellows); natural iron oxides; chromium oxide;cobalt blue; cobalt green; titanium dioxide and carbon black (concretegrade).

Preferably, the first aspect of the invention provides a flowable, spraydried, particulate formulation consisting essentially of one or moreinorganic pigments, poly(ethylene glycol), hydroxylated amine andpolycarboxylic acid in admixture.

Preferably, the formulation comprises poly(ethylene glycol),polycarboxylic acid dispersant and hydroxylated amine in a 2-6:2-6:1ratio by weight. More preferably, the formulation comprisespoly(ethylene glycol), polycarboxylic acid dispersant and hydroxylatedamine in a 2-4:4-6:1 ratio by weight. Most preferably, the formulationcomprises in admixture poly(ethylene glycol), polycarboxylic aciddispersant and hydroxylated amine in a 3:5:1 ratio by weight.

Preferably, the poly(ethylene glycol) has a median molecular weight inthe range 7,000 to 9,000 (PEG 8000).

Preferably, the hydroxylated amine is 2-amino-2-methyl-1-propanol. Apreferred 2-amino-2-methyl-1-propanol is supplied under the trade nameAMP 95™ (CAS#124-68-5).

Preferably, the polycarboxylic acid dispersant is a carboxylated acrylicco-polymer. A preferred acrylic acid polymer is supplied under the tradename RHODOLINE 226/40™ (CAS# 9003-04-7).

Preferably, the polycarboxylic acid is less than 5% by weight of theformulation.

Preferably, the formulation consists essentially of the one or moreinorganic pigments, the poly(ethylene glycol), the polycarboxylic aciddispersant and the hydroxylated amine in a 45-160:2-6:2-6:1 ratio byweight. More preferably, the formulation consists essentially of the oneor more pigments, the poly(ethylene glycol), the polycarboxylic aciddispersant and the hydroxylated amine in a 45-125:2-6:2-6:1 ratio byweight. Yet more preferably, the formulation consists essentially of theone or more pigments, the poly(ethylene glycol), the polycarboxylic aciddispersant and the hydroxylated amine in a 45-110:2-6:2-6:1 ratio byweight. Most preferably, the formulation consists essentially of the oneor more pigments, the poly(ethylene glycol), the polycarboxylic aciddispersant and the hydroxylated amine in a 45-110:3:5:1 ratio by weight.

Preferably, the particles of the formulation are of a hollow doughnutmorphology with a median diameter in the range 20 to 150 μm. Morepreferably, the particles of the formulation are of a hollow doughnutmorphology with a median diameter of 30 to 50 μm.

In a preferred embodiment of the first aspect the invention provides acolourant product that is a flowable, spray-dried, particulateformulation consisting essentially of 85 to 95% by weight of one or moreinorganic pigments, 3 to 7% by weight of poly(ethylene glycol) having amedian molecular weight in the range 7,000 to 9,000 (PEG 8000), 3 to 6%by weight carboxylated acrylic co-polymer dispersant and 0.5 to 2.0% byweight hydroxylated amine.

In a second aspect the invention provides a method of colouring acementitious building material comprising the step of mixing aformulation of the first aspect of the invention with a cementitiouspremix.

Preferably, the cementitious premix is hydrated immediately prior to thestep of mixing the formulation with the cementitious premix. Morepreferably, the cementitious premix is a floor levelling or repairproduct.

Preferably, the cementitious building material is selected from thegroup consisting of: concrete, mortar and plaster.

In a third aspect the invention provides an integrally colouredcementitious building material comprising one or more pigments,poly(ethylene glycol), polycarboxylic acid and hydroxylated amine.

Preferably, the cementitious building material is selected from thegroup consisting of: concrete, mortar and plaster. More preferably, thebuilding material is concrete. Most preferably, the building material isa levelled or repaired concrete floor.

In the description and claims of this specification the followingacronyms, terms and phrases have the meaning provided: “admixture” meansan intimate, uniform mixture of two or more components; “buildingmaterial” means a hardened cementitious material including concrete,mortar and plaster; “calcining” means reducing, oxidising or desiccatingby roasting or strong heat; “cement” means a powdery substance made bycalcining lime and clay used in making mortar and concrete;“cementitious building material” means a building material prepared bymixing cement and water with or without the addition of aggregate orsand; “cementitious premix” means a mixture of cement and water used inthe forming of a building material such as concrete, mortar or plaster;“colourant” means a formulation including primary particles of one ormore pigments used in preparing a coloured base medium such as acementitious building material “colouring” means dispersing one or morepigments uniformly throughout a building material and “coloured” has acorresponding meaning; “comprising” means “including”, “containing” or“characterized by” and does not exclude any additional element,ingredient or step; “concrete” means a building material made from amixture of ingredients including gravel, sand, cement and water forminga stone-like mass on hardening; “consisting of” means excluding anyelement, ingredient or step not specified except for impurities andother incidentals; “consisting essentially of” means excluding anyelement, ingredient or step that is a material limitation; “copolymer”means a polymer formed by the polymerization of two or more differentmonomers; “flowable” means capable of being poured from a container orpackage; “formula” means a list of ingredients with which a formulationis prepared; “formulant” means an ingredient used in the preparation ofa formulation; “formulation” means a material or mixture preparedaccording to a formula; “hydrophilic” means having a tendency to mixwith, dissolve in, or be wetted by water; “hydrophobic” means having atendency to repel or fail to mix with water; “integrally coloured” meansparticles of pigment are distributed throughout the body of thematerial; “mortar” means a mixture of cement and water used in buildingto bond bricks or stones; “pigment” means a material or substance usedfor colouring; “plaster” means a mixture of sand and cement andsometimes lime with water, for spreading on walls, ceilings, or otherstructures, to form a smooth hard surface when dried; “plurality” meanstwo or more; “premix” means a flowable mixture used in the preparationof a building material prior to mixing with water (hydration); “primaryparticles” means the smallest particles of a comminuted material orsubstance; “product” means a formulation packaged and identified for aspecified use; “synthetic” means prepared by chemical synthesis.

The terms “first”, “second”, “third”, etc. used with reference toelements, features or integers of the subject matter defined in theStatement of Invention and Claims, or when used with reference toalternative embodiments of the invention are not intended to imply anorder of preference.

Where the presence, concentration or a ratio of ingredients is specifiedthe presence, concentration or ratio specified is the initial presence,concentration. Where values are expressed to one or more decimal placesstandard rounding applies. For example, 1.7 encompasses the range 1.650recurring to 1.7499 recurring.

The invention will now be described with reference to embodiments orexamples and the figures of the accompanying drawings pages. Throughoutthe following description the term “colourant” is used to refer to theformulations of the examples.

BRIEF DESCRIPTION OF DRAWING

FIG. 1. Heat output curves for mortars prepared using cement sourcedfrom Golden Bay (plots 2 and 4) or Holcim (plots 1 and 3) with (plots 1and 2) or without (plots 3 and 4) the addition of 2% (w/w) of asuperplasticiser (CD31).

FIG. 2. Schematic representation of a single-point dischargeconfiguration of a spray dryer (1) of the type used in the methodsdescribed provided with an inlet (2), an outlet (3) and a rotaryatomiser (4).

FIG. 3. Heat output curves for coloured mortars prepared usingunformulated pigments and corresponding formulations prepared accordingto the invention. Heat output curves are shown overlain on the heatoutput curve for unadulterated cement (Control). All mortars wereprepared using cement sourced from Golden Bay.

FIG. 4. Heat output curves for coloured mortars prepared usingunformulated pigments and corresponding formulations. Heat output curvesare shown overlain on the heat output curve for unadulterated cement(Control). All mortars were prepared using cement sourced from Holcim.

FIG. 5. Heat output curves for coloured mortars prepared usingunformulated pigments and corresponding formulations prepared accordingto the invention. Heat output curves are shown overlain on the heatoutput curve for unadulterated cement (Control), All mortars wereprepared using cement sourced from Dricon.

FIG. 6. Photographs of samples of the hardened cementitious floorlevelling product SIKA™ LEVEL 30 (Sika (NZ) Limited) with (A) andwithout (B) the addition of colourant.

DETAILED DESCRIPTION

The hydration of cementitious premixes by the addition of waterinitiates ettringite formation. This primary ettringite formation isimportant in the hardening and setting of concrete and is to bedistinguished from the delayed ettringite formation associated withdamage to hardened concrete. During the first hours of hydration theshape and size of the ettringite crystals is influenced by thecomposition of the alkaline solution in which the crystals are forming.The hardening and setting of concrete can be monitored by calorimetricmethods.

In addition to their ability to effectively disperse the primaryparticles of inorganic pigments, the selection of formulants for use inthe colouring of concrete must also consider the potentially deleteriouseffect the presence of the formulants in the alkaline solution will haveon primary ettringite formation. The formulants used in cementitiousbuilding materials are often observed to influence the characteristicsof primary ettringite formation (FIG. 1).

A deleterious effect on primary ettringite formation is likely to beexacerbated when colouring cementitious premixes formulated for use asrapid setting floor levelling and repair products. These products aredesigned to find their own levels when installed at a thickness of 3 mmor greater. Once hydrated and poured the cementitious mix hardens andsets rapidly so that it can be walked on within as little as two tothree hours. The cementitious premixes used in floor levelling andrepair are formulated with specially selected polymers to provide theseperformance characteristics.

The invention resides partly in the selection of a combination offormulants that do not have a significant deleterious effect on thehardening and setting of cementitious building materials when mixed witha hydrated cementitious premix. The invention also resides partly inthis combination of formulants being compatible with the spray drying ofaqueous formulations of the inorganic pigments used in colouringcementitious building materials. The invention permits the formulationof a range of these pigments as flowable granules of uniform densitythat may be dispensed gravimetrically or volumetrically, therebyfacilitating the use of these pigments in colouring cementitiousbuilding materials.

The invention will be illustrated with reference to the use of thecombination of a poly(ethylene glycol), a polycarboxylic acid and ahydroxylated amine in the preparation of flowable, spray dried,particulate formulations of inorganic pigments that readily dispersewhen added to hydrated cementitious premixes. The use of thiscombination of formulants does not adversely affect the primaryettringite formation as evidenced by no observed deleterious effects onthe hardening and setting of the building material.

Preparation of Colourants

The flowable, spray dried, particulate formulations are prepared bydispersing the pigments in an aqueous solution of the formulants.Dispersions of different pigments may be blended if desired prior tospray drying. A schematic representation of single-point dischargeconfiguration of a spray dryer fitted with a rotary atomiser is providedin FIG. 2.

EXAMPLES Example 1

A solution of poly(ethylene glycol) 8,000 g/mol (PEG 8000) in water wasprepared at a ratio of 10% (w/w) by dissolving 90 g of the PEG 8000 in900 g of water with gentle agitation. The solution was then blended with150 g of a polycarboxylic acid dispersant (RHODOLINE 226/40) and 30 g ofa hydroxylated amine (AMP 95). Following homogenisation of the blendedmix using a high speed disperser, 3,000 g of green oxide pigment wasslowly added with continuous stirring up to 3,000 rpm for a total of 80minutes to provide a homogenous dispersion. The homogenous dispersionwas then spray-dried using a GEA Niro MOBILE MINOR™ (GEA ProcessEngineering) equipped with a rotary atomiser (channel wheel, 20,000 rpm)in a single-point discharge configuration and operated at an inlettemperature of 185° C. and outlet temperature of 95° C. A particulateformulation of hollow doughnut morphology with a median particlediameter of 30 μm was obtained at a rate of 1.9 Kg/hour (1.2% w/wmoisture content) with 52% yield.

Example 2

A selection of poly(ethylene glycol) 8,000 g/mol (PEG 8000) in water wasprepared at a ratio of 6% (w/w) by dissolving 75 g of the PEG 8000 in1250 g of water with gentle agitation. The solution was then blendedwith 125 g of a polycarboxylic acid dispersant (RHODOLINE™ 226/40) and25 g of a hydroxylated amine (AMP 95). Following homogenisation of theblended mix using a high speed disperser, 2,500 g of red ochre pigmentwas slowly added to provide a raw homogenous dispersion. The rawhomogenous dispersion was then ball-milled for a total of 12 hours toprovide a final milled homogenous dispersion. The homogenous dispersionwas then spray-dried using a GEA Niro MOBILE MINOR™ (GEA ProcessEngineering) equipped with a rotary atomiser (channel wheel, 20,000 rpm)in a single-point discharge configuration and operated at an inlettemperature of 185° C. and outlet temperature of 95° C. A particulateformulation of hollow doughnut morphology with a median particlediameter of 30 μm was obtained at a rate of 1.9 Kg/hour (1.2% w/wmoisture content) with 52% yield.

Similar quantities of colourants (Examples 3 to 6) were prepared bymethods similar to those employed for the preparation of the colourantsof Example 1 and Example 2. Larger quantities of colourants (Examples 7to 9) were prepared using a GEA Niro VERSATILE-SD™ 6.3N (GEA ProcessEngineering).

The colourant of Example 7 was spray-dried with an inlet temperature of230° C. and an outlet temperature of 85° C. at a production rate of 23Kg/h with a pressure nozzle configuration and final moisture content ofless than 1.5%.

The colourant of Example 8 was spray-dried with an inlet temperature of230° C. and an outlet temperature of 95° C. at a production rate of 55Kg/h with a pressure nozzle configuration and final moisture content ofless than 1.5%.

The colourant of Example 9 was spray-dried with an inlet temperature of220° C. and an outlet temperature of 90° C. at a production rate of 60Kg/h with a pressure nozzle configuration and final moisture content ofless than 1.5%.

Example 3

Ingredient (with 300 g water) Quantity (g) Ratio Bluish red iron oxide(R5580) 718.0 160 Poly(ethylene glycol) (PEG 400) 26.0 5.8Polycarboxylic acid dispersant 26.6 5.9 (RHODOLINE ™ 226/40)Hydroxylated amine (AMP 95) 4.5 1

Example 4

Ingredient (with 211 g water) Quantity (g) Ratio Dark brown iron oxide(Umber 190) 645.0 53 Fumed silica (Aerosil 200) 3.9 Poly(ethyleneglycol) (PEG 400) 50.0 4.0 Polycarboxylic acid dispersant 40.0 3.3(RHODOLINE ™ 226/40) Hydroxylated amine (AMP 95) 12.3 1

Example 5

Ingredient (with 390 g water) Quantity (g) Ratio Natural red iron oxide(Kremer 48600) 520.0 75 Fumed silica (Aerosil 200) 3.8 Poly(ethyleneglycol) (PEG 400) 16.6 2.4 Polycarboxylic acid dispersant 20.0 2.9(RHODOLINE ™ 226/40) Hydroxylated amine (AMP 95) 7.0 1

Example 6

Ingredient (with 275 g water) Quantity (g) Ratio English red light ironoxide (Kremer 40542) 771.0 114 Fumed silica (Aerosil 200) 5.0Poly(ethylene glycol) (PEG 400) 26.0 3.8 Polycarboxylic acid dispersant31.0 4.6 (RHODOLINE ™ 226/40) Hydroxylated amine (AMP 95) 6.8 1

Example 7

Ingredient (with 1431.8 Kg water) Quantity (Kg) Ratio Carbon black 954.5100 Poly(ethylene glycol) (PEG 8000) 28.6 3 Polycarboxylic aciddispersant 38.2 4 (RHODOLINE ™ 226/40) Hydroxylated amine (AMP 95) 9.5 1

Example 8

Quantity Ingredient (with 111.6 Kg water) (Kg) Ratio Iron oxide red (Red5530)(Nubolia) (CAS# 1309-37-1) 450.3 100 Poly(ethylene glycol) (PEG8000) 13.5 3 Polycarboxylic acid dispersant (RHODOLINE 226/40) 20.1 4.5Hydroxylated amine (AMP 95) 4.5 1

Example 9

Ingredient (with 42.49 Kg water) Quantity (Kg) Ratio Iron oxide red (Red5530)(Nubolia) 73.4 100 (CAS# 1309-37-1) Iron oxide yellow (Yellow 5021)39.5 (Bayferrox)(CAS# 51274-00-1) Poly(ethylene glycol) (PEG 8000) 3.393 Polycarboxylic acid dispersant 5.08 4.5 (RHODOLINE ™ 226/40)Hydroxylated amine (AMP 95) 1.13 1

Comparative Examples

To evaluate the effect of varying the concentrations and ratios of theingredients on performance a series of spray-dried colourants wereprepared of the following composition:

TABLE 1 Compositions of a series of spray-dried colourants comprisingchrome green oxide as the pigment. Ingredient G1 G2 G3 G4 G5 G6 G7Poly(ethylene glycol) 6 6 6 6 6 3 14.4 (PEG 8000) Polycarboxylic aciddispersant 1.4 3.6 5 7.5 5 5 6 (RHODOLINE ™ 226/40) Hydroxylated amine 11 1 1 5 1 1.2 (AMP 95) The quantities of the ingredients are expressedas a percentage by weight of the pigment.

Each one of the spray-dried colourants from the series was evaluated bymixing at a rate of 2% (w/w) with a slurry of cementitious buildingmaterial consisting of 225 g water, 500 g dry sand and 1,000 g ordinaryPortland cement.

Yellowing of the surface of the pigmented building material preparedfrom colourant G4 indicated an upper limit for inclusion of theingredient RHODOLINE 226/40 of 5% by weight. The best handling andperformance characteristics were observed for colourants G1 and G5indicating a preferred ratio by weight of the ingredient RHODOLINE226/40 to AMP-95 of around 1.

Other ingredients were evaluated as alternatives to the use ofpoly(ethylene glycol) as a formulant. As before batches of trialformulations were spray-dried using either the GEA Niro MOBILE MINOR™(GEA Process Engineering) or a Mini Spray Dryer B-290 (Buchi).Spray-drying parameters were optimised for each trial formulation. Theingredients employed in these other formulations and observationsconcerning the performance of the product of spray-drying are providedas comparative examples only and are not embodiments of the invention.

Comparative Example 1

Ingredient (with 114.6 g water) Quantity (g) Yellow iron oxide (pigmentcode PY42) 91.3 (CAS# 51274-00-1) Sodium silicate 2.1 Polycarboxylicacid dispersant 0.6 (RHODOLINE ™ 226/40) Hydroxylated amine (AMP 95) 0.4

The formulation was spray-dried using the Mini Spray Dryer B-290 (Buchi)with an inlet temperature of 180° C. and an outlet temperature of 105°C. The product of spray-drying would not disperse when added to anaqueous slurry of concrete. This was attributed to a surface layer ofsodium silicate not hydrating rapidly enough to release the primaryparticles of pigment.

Comparative Example 2

Ingredient (with 1258.1 g water) Quantity (g) Yellow iron oxide (pigmentcode PY42) 1979.7 (CAS# 51274-00-1) Titanium dioxide 1979.7 682 5.5Polydextrose 407.0 Polycarboxylic acid dispersant 36.0 (RHODOLINE ™226/40) Hydroxylated amine (AMP 95) 10.7

The formulation was spray-dried using the GEA Niro MOBILE MINOR™ with aninlet temperature of 180° C., an out let temperature of 95° C. and aspindle speed of 15,000 rpm. The product of spray-drying was mixed at arate of 3% (w/w) with a slurry of cement (1:2 (w/w) water-cement)comprising no aggregate. Hydration of the cementitious mix was found tobe indefinitely retarded.

Comparative Example 3

Ingredient (with 150 g water) Quantity (g) GO 200 Polyvinyl alcohol(MONOSOL ™) 12 Polycarboxylic acid dispersant (RHODOLINE ™ 226/40) 9Hydroxylated amine (AMP 95) 3

The formulation was spray-dried using the Mini Spray Dryer B-290 (Buchi)with an inlet temperature of 180° C. and an outlet temperature of 105°C. The product of spray-drying was mixed at a rate of 4% (w/w) with aslurry of cement (1:2 (w/w) water-cement). Product prepared with eitherof the trade name products MONOSOL™ 8900 or MONOSOL™ BP-3 both displayedpoor handling characteristics accompanied by foam generation andretention in the admixture.

Evaluation of Colourants

The colourants of Example 3, Example 4, Example 5 and Example 6 wereevaluated for use in colouring concrete or mortar prepared using cementfrom three different sources (Golden Bay, Holcim and Dricon). Thecolourants were evaluated against their corresponding unformulatedpigments (milled iron oxides) with (Example 4, Example 5 and Example 6)or without (Example 3) the addition of fumed silica. The colourants wereevaluated for any adverse effects on the setting and hardeningcharacteristics of the resulting cementitious building materialcalorimetry was used to evaluate early age hydration of the cementitiousbuilding material. Compressive strengths of 50 mm cubes of cement mortarwas determined at 48 hours, 7 days and 28 days.

Calorimetry

Heat output curves for coloured mortars prepared using the differentsources of cement are presented in FIG. 3 (Golden Bay), FIG. 4 (Holcim)and FIG. 5 (Dricon). The absence of any significant variation betweenthe heat flows measured confirms the compatibility between thecolourants with the cementitious building material. By contrast, theeffect on heat flows of the addition of a commonly used plasticizer (2%by weight of DC31) is shown in FIG. 1.

Compressive Strength

Colourants were added at a rate of 3% by weight to a slurry of cement(0.4 (w/w) water-cement) and the compressive strength of hardened blocks(50×50×50 mm) determined. Slurries were prepared using cement sourcedfrom either Golden Bay or Holcim. The compressive strength determinedfor coloured hardened blocks prepared using these two sources of cementare presented in Table 2 (Golden Bay) and Table 3 (Dricon). Compressivestrengths were also determined for coloured hardened blocks prepared bythe addition of colourant at a rate of 3% by weight to a slurry ofcement and sand (0.4 (w/w) water-cement and 1.5 (w/w) sand-cement). Thecompressive strengths determined for the coloured hardened blocks arepresented in Table 4 (Golden Bay) and Table 5 (Dricon). The moderatereduction in strength (circa 10%) may be readily compensated for byaddition of cement to the premix.

TABLE 2 Compressive strengths at 48 hours, 7 days and 28 days followinghydration of coloured (3% (w/w) colourant) and uncoloured (control)hardened blocks prepared using cement (0.4 (w/w) water-cement) sourcedfrom Golden Bay. Colourant 48 hours 7 days 28 days Control 39.7 56.573.0 Example 3 40.3 57.6 75.5 Example 4 38.9 59.4 73.6 Example 5 39.360.5 80.3 Example 6 38.0 57.7 74.4

TABLE 3 Compressive strengths at 48 hours, 7 days and 28 days followinghydration of coloured (3% (w/w) colourant) and uncoloured (control)hardened blocks prepared using cement (0.4 (w/w) water-cement) sourcedfrom Dricon. Colourant 48 hours 7 days 28 days Control 43.4 59.1 78.8Example 3 41.0 54.4 70.6 Example 4 39.8 53.4 67.3 Example 5 42.6 57.272.5 Example 6 38.2 50.1 65.2

TABLE 4 Compressive strengths at 7 days and 28 days following hydrationof coloured (3% (w/w) colourant) and uncoloured (control) hardenedblocks prepared using a 1.5 (w/w) mixture of sand and cement (0.4 (w/w)water-mixture). The cement was sourced from Golden Bay. Sample 7 days 28days Control 52.1 61.9 Example 3 47.8 57.6 Example 4 42.4 54.9 Example 546.9 57.5 Example 6 46.7 59.0

TABLE 5 Compressive strengths at 7 days and 28 days following hydrationof coloured (3% (w/w) colourant) and uncoloured (control) hardenedblocks prepared using a 1.5 (w/w) mixture of sand and cement (0.4 (w/w)water-mixture). The cement was sourced from Dricon. Sample 7 days 28days Control 46.4 57.9 Example 3 46.3 62.5 Example 4 36.9 61.2 Example 549.5 62.2 Example 6 47.6 59.0

Colouring of Self-Levelling Cementitious Floor Coverings

The surface of a contained area of floor substrate was cleaned andprepared according to the supplier's instructions prior to pouring ofthe cementitious floor levelling product SIKA™ LEVEL 30 (Sika (NZ)Limited). The colourant was added to the water used in mixing of theproduct at a ratio of 2% (w/w) of the product. The coloured concrete wasthen applied to the cleaned and prepared surface of the floor substrate.By contrast with commercially available formulations of iron oxide theaddition of the colourant had no significant effect on air entrainment,workability, or curing and setting times. Photographs of samples ofcoloured and uncoloured white cement are provided in FIG. 6. Althoughprovided in greyscale the photographs show the uniform distribution ofthe pigment throughout the hardened concrete.

Although the invention has been described with reference to embodimentsor examples it should be appreciated that variations and modificationsmay be made to these embodiments or examples without departing from thescope of the invention. Where known equivalents exist to specificelements, features or integers, such equivalents are incorporated as ifspecifically referred to in this specification. In particular,variations and modifications to the embodiments or examples that includeelements, features or integers disclosed in and selected from thereferenced publications are within the scope of the invention unlessspecifically disclaimed. The advantages provided by the invention anddiscussed in the description may be provided in the alternative or incombination in these different embodiments of the invention.

REFERENCED PUBLICATIONS

Anon (2010) Standard Specification for Pigments for Integrally ColouredConcrete (C959/C959M) ASTM International, 100 Bar Harbour Drive, PO BoxC 700, West Conshohocken, Pa. 19428-2959, U.S.

Bowen (1980) Cement Colouring Composition and Method of Producing SameU.S. Pat. No. 4,204,876.

Dunnous and Yocum (2004) Product and Method for Colouring Concrete U.S.Pat. No. 6,695,990.

Hertz et al (2012) Concrete Colouring Compositions and Methods U.S.patent application Ser. No. 13/345,200 (publ. no. US 2012/0247372 A1).

Johansen et al (1999) Method of Using a Colouring Composition in aConcrete-Based Composition U.S. Pat. No. 5,951,752.

Jungk (1990) Process for Dyeing Concrete U.S. Pat. No. 4,946,505.

Kohler et al (1998) Preparation and Use of Iron Oxide Black PigmentGranules U.S. Pat. No. 5,718,755.

Krockert and Linde (1993) Process for Colouring Building Materials U.S.Pat. No. 5,215,583.

Linde and Eitel (1996) Process for the Colouration of Building MaterialsU.S. Pat. No. 5,484,481.

Noack and Herrmann (2004) Colouring Pigment Granulates and Method forProducing the Same U.S. Pat. No. 6,824,604.

Supplee (2003) Concrete Admixture with Improved Durability andEfflorescence Control Containing a Highly Resilient Colourant U.S. Pat.No. 6,537,366.

Supplee (2007) Integral or Shake-on Colourant Admixture with ImprovedColour Durability in Concrete and Other Cementitious Systems UsingHighly Resilient Colourants Organic or Oxide in Nature U.S. patentapplication Ser. No. 11/760,421 (publ. no. US 2007/0294843 A1).

Tomkinson (1971) Iron Oxide Pigments U.S. Pat. No. 3,619,227.

Will (1998) Process for Colouring Concrete Using Compacted InorganicGranules U.S. Pat. No. 5,853,476.

1. A flowable, spray dried, particulate formulation suitable for use incolouring cementitious building materials comprising in admixture one ormore inorganic pigments, poly(ethylene glycol), hydroxylated amine andpolycarboxylic acid.
 2. A flowable, spray dried, particulate formulationsuitable for use in colouring cementitious building materials consistingessentially of one or more inorganic pigments, poly(ethylene glycol),hydroxylated amine and polycarboxylic acid in admixture.
 3. Theformulation of claim 1 or 2 where the one or more pigments of theformulation are inorganic pigments selected from the group consistingof: synthetic iron oxides (black, browns, red and yellows); natural ironoxides; chromium oxide; cobalt blue; cobalt green; titanium dioxide andcarbon black (concrete grade).
 4. The formulation of any one of claims 1to 3 where the formulation comprises poly(ethylene glycol),polycarboxylic acid dispersant and hydroxylated amine in a 2-6:2-6:1ratio by weight.
 5. The formulation of claim 4 where the formulationcomprises poly(ethylene glycol), polycarboxylic acid dispersant andhydroxylated amine in a 2-4:4-6:1 ratio by weight.
 6. The formulation ofclaim 5 where the formulation comprises in admixture poly(ethyleneglycol), polycarboxylic acid dispersant and hydroxylated amine in a3:5:1 ratio by weight.
 7. The formulation of any one of claims 1 to 6where the poly(ethylene glycol) has a median molecular weight in therange 7,000 to 9,000 (PEG 8000).
 8. The formulation of any one of claims1 to 7 where the hydroxylated amine is 2-amino-2-methyl-1-propanol. 9.The formulation of any one of claims 1 to 8 where the polycarboxylicacid is a carboxylated acrylic co-polymer.
 10. The formulation of anyone of claims 1 to 9 where the polycarboxylic acid is less than 5% byweight of the formulation.
 11. The formulation of any one of claims 1 to10 where the formulation consists essentially of the one or morepigments, the poly(ethylene glycol), the polycarboxylic acid dispersantand the hydroxylated amine in a 45-160:2-6:2-6:1 ratio by weight. 12.The formulation of claim 11 where the formulation consists essentiallyof the one or more pigments, the poly(ethylene glycol), thepolycarboxylic acid dispersant and the hydroxylated amine in a45-125:2-6:2-6:1 ratio by weight.
 13. The formulation of claim 12 wherethe formulation consists essentially of the one or more pigments, thepoly(ethylene glycol), the polycarboxylic acid dispersant and thehydroxylated amine in a 45-110:2-6:2-6:1 ratio by weight.
 14. Theformulation of any one of claims 1 to 13 where the particles of theformulation are of a hollow doughnut morphology with a median diameterin the range 20 to 150 μm.
 15. The formulation of claim 14 where theparticles of the formulation are of a hollow doughnut morphology with amedian diameter of 30 to 50 μm.
 16. A method of colouring a cementitiousbuilding material comprising the step of mixing a formulation of any oneof claims 1 to 15 with a cementitious premix.
 17. The method of claim 16where the cementitious premix is hydrated immediately prior to the stepof mixing the formulation with the cementitious premix.
 18. The methodof claim 17 where the cementitious premix is a floor levelling or repairproduct.
 19. An integrally coloured cementitious building materialcomprising one or more pigments, poly(ethylene glycol), hydroxylatedamine and polycarboxylic acid.
 20. The cementitious building material ofclaim 19 where the cementitious building material is concrete.